US7465324B2 - Process for obtaining a heating fluid as indirect heat source for carrying out reforming reactions - Google Patents

Process for obtaining a heating fluid as indirect heat source for carrying out reforming reactions Download PDF

Info

Publication number
US7465324B2
US7465324B2 US09/802,925 US80292501A US7465324B2 US 7465324 B2 US7465324 B2 US 7465324B2 US 80292501 A US80292501 A US 80292501A US 7465324 B2 US7465324 B2 US 7465324B2
Authority
US
United States
Prior art keywords
flow
water
heating fluid
oxygen
hydrocarbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime, expires
Application number
US09/802,925
Other languages
English (en)
Other versions
US20010025449A1 (en
Inventor
Ermanno Filippi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Casale SA
Original Assignee
Ammonia Casale SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ammonia Casale SA filed Critical Ammonia Casale SA
Assigned to AMMONIA CASALE S.A. reassignment AMMONIA CASALE S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FILIPPI, ERMANNO
Publication of US20010025449A1 publication Critical patent/US20010025449A1/en
Application granted granted Critical
Publication of US7465324B2 publication Critical patent/US7465324B2/en
Adjusted expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/34—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents
    • C01B3/38—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts
    • C01B3/384—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air by reaction of hydrocarbons with gasifying agents using catalysts with external heating of the catalyst
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B3/00—Other methods of steam generation; Steam boilers not provided for in other groups of this subclass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/0285—Heating or cooling the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00017—Controlling the temperature
    • B01J2208/00389—Controlling the temperature using electric heating or cooling elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0816—Heating by flames
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0822—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel the fuel containing hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • C01B2203/0827—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel at least part of the fuel being a recycle stream
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866—Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency

Definitions

  • the present invention relates to a process for obtaining a heating fluid as indirect heat source for carrying out endothermic reactions, such as hydrocarbon reforming reactions.
  • the present invention relates to a process comprising the steps of:
  • the present invention also relates to a process for carrying out hydrocarbon reforming reactions in an exchanger type reformer.
  • hydrocarbons it is generally intended to mean light gaseous hydrocarbons (C1-C4) such as methane, natural gas, refinery gas, or light liquid hydrocarbons, such as naphtha, and their mixtures.
  • gas flow comprising oxygen It is generally intended to mean air, air enriched with oxygen or pure oxygen.
  • exchanger type reformer relates to a particular apparatus suited to carry out reforming of hydrocarbons. From a conceptual point of view, this apparatus can be compared to a heat exchanger.
  • the reforming reaction is carried out in a plurality of tubes (tube bundle) filled with catalyst and crossed by the flow of hydrocarbons and water vapour.
  • the reaction heat is supplied through indirect heat exchange from a heating fluid licking the tubes on the mantel side.
  • the heat needed by the reforming reaction is generally provided in the exchanger type reformer (primary reformer) through indirect heat exchange with the hot gas exiting from the secondary reforming equipment.
  • reaction heat is provided through direct heat exchange of the heat produced by the exothermic combustion reaction of an oxidizing agent with part of the hydrocarbons and of the hydrogen which are in the apparatus.
  • the oxidizing agent in such secondary reformer is generally air, and the amount of nitrogen introduced together with such oxidizing agent must be the stoichiometric one for the following NH 3 synthesis reaction, the amount of heat available for the exchanger type reformer is fixed and anyway not enough to allow a satisfying reforming of the hydrocarbons.
  • the first solution implies the drawback of having to compress an amount of air largely exceeding the stoichiometric amount (about 50% more). Moreover, the nitrogen in excess will not be used in the synthesis reaction, and therefore must be eliminated with expensive systems; in alternative, it may be let reach the ammonia synthesis loop, from which it has to be purged, and in this case it is noxious to the synthesis reaction. In both situations, the energy used for the compression of the nitrogen in excess is lost, increasing by consequence the energy consumption.
  • the second solution implies the burden of an air enrichment system, which is expensive and takes up a relevant amount of energy.
  • the so obtained heating fluid shall flow in the exchanger type reforming unit with a pressure substantially equivalent to that of the reactant gases (for example about 25 bar in case of hydrogen).
  • thermodynamic efficiency lower than 100%, typically around 70%.
  • the energy consumption are further increased by the very high air flow rate to be compressed since it is necessary to run with a strong excess of air (about 100%) the combustion reaction for obtaining the heating fluid.
  • the flame temperature inside the combustor is reduced down to acceptable values for the so obtained heating fluid not to damage the exchanger type reformer in which the reforming reaction takes place.
  • the overall efficiency of the compression and expansion cycle of the heating fluid is equal to the product of the compressor and turbine efficiency, that is 70% multiplied by 70% equals about 50%. This means that about half of the energy used to compress the heating fluid is lost.
  • the high energy consumption resulting from the reforming processes with indirect heat exchange with a heating fluid does not relate so much to the reforming process in se, but to the compression and expansion steps needed for obtaining and making a heating fluid suitable for being employed in such process circulate.
  • the technical problem underlying the present invention is that of providing a process for obtaining a heating fluid to be used as heat source in hydrocarbon reforming reactions, that allows on one side to realise a reforming process which uses the exchanger type reformer as reforming apparatus, ameliorating its performance in terms of reliability and maintenance costs, and at the same time allows an overall energy consumption as low as possible and anyway lower than that of the conventional reforming processes which employ kiln reformers.
  • the above problem is solved by a process of the above mentioned type, which is characterised in that it further comprises the step of feeding a flow comprising water, preferably in the form of vapour, to the fluid at high temperature and/or to the combustor.
  • Such phenomenon is a destructive and fast corrosion of the parts of the equipment subjected to high temperatures, for example between 400 and 800° C., and to a reducing atmosphere comprising carbon monoxide.
  • the metal dusting is a phenomenon, which up to now has not been fully explained and is often unforeseeable. It comes from the so called “Boudouard” equilibrium, that is to say from the reaction between two molecules of carbon monoxide that produces a molecule of carbon dioxide and a molecular of free carbon.
  • the free carbon in the above mentioned conditions of high temperature and reducing atmosphere, variously combines with the metals, breaking down their crystalline structure and causing a localised metal dusting.
  • the heating fluid fed to the exchanger type reformer advantageously comprises a certain amount of water or water vapour. This makes the atmosphere of that portion of the exchanger type reforming apparatus licked by the heating fluid oxidant enough to prevent the metal dusting from taking place, to all advantage of a higher reliability of the reforming equipment and lower maintenance costs.
  • the process according to the present invention allows also to drastically reduce the energy consumption of the compression and expansion steps required for obtaining the heating fluid and its circulation in the reforming plant, accordingly reducing in an easy and extremely effective way the overall energy consumption.
  • the flow comprising water is fed into the combustor as vapour together with the flow comprising oxygen.
  • the present process advantageously provides the steps of:
  • liquid water may be pumped with extremely low energy consumption into the gas flow comprising oxygen. Only afterwards the water will be evaporated at relatively low temperatures, preferably around 300° C., exploiting heat sources already available in the process.
  • the process for obtaining the heating fluid provides the compression only of the flow gas comprising hydrocarbons and of the gas flow comprising air, preventing in this way the compression of the water vapour.
  • the flow comprising water in the form of vapour fed to the combustor or directly to the high temperature heating fluid leaving the combustor does not require relevant energy consumption since it is advantageously produced by evaporating water at a predetermined pressure, i.e. previously pumped water flowing at a pressure substantially corresponding to the process pressure.
  • the water vapour present in the heating fluid which has been obtained with low energy consumption, is expanded together with the rest of the burnt gases, thus participating in remarkably increasing the flow rate of such fluid with a particularly advantageous energy recovery.
  • thermodynamic cycle efficiency is advantageously observed in the various compression and expansion steps for obtaining a heating fluid and for the circulation thereof. This advantageously reflects in a drastic decrease of energy consumption.
  • the process according to the present invention allows achieving a saving up to 20% in the consumption of hydrocarbons (methane) to be burnt for obtaining the heating fluid, with respect to the above described processes according to the prior art.
  • the smaller amount of hydrocarbons to be burnt and hence to be compressed allows carrying out the compression of the gas flow comprising oxygen with a power up to 65% less than the compression power required by the prior art, with ensuing relevant savings in terms of energy consumption and investment costs.
  • FIG. 1 shows in a general and schematic way a block diagram of a process for the reforming of hydrocarbons by indirect heat exchange with a heating fluid, wherein there is outlined the process for obtaining such heating fluid according to a preferred embodiment of the present invention
  • FIG. 2 shows a schematic longitudinal cross section view of an exchanger type reforming apparatus.
  • a block diagram of a process for hydrocarbon reforming is generally indicated with 1; in such process the reaction heat is provided through indirect heat exchange with a heating fluid.
  • a process of this type comprises both the actual hydrocarbon reforming process, which relates to the conversion of hydrocarbons in basic chemical compounds, such as hydrogen, carbon monoxide and carbon dioxide, and the process for obtaining the heating fluid that will provide the reaction heat during the hydrocarbon reforming.
  • FIG. 1 only the main process steps have been shown, unessential details for carrying out the present invention and/or those already known to a man skilled in the art having been cut out.
  • blocks 10 - 12 indicate a process water vapour source (block 10 ), a compression step of a flow comprising hydrocarbons (block 11 ) and a reforming step of hydrocarbons (block 12 ), respectively.
  • the flow lines indicate a gas flow comprising water vapour (flow line 1 ), a flow comprising hydrocarbons (flow lines 2 , 2 a ), a flow comprising hydrocarbons and water vapour (flow line 3 ) and a gas flow comprising hydrogen (flow line 4 ), respectively.
  • process water vapour source (block 10 ), it is meant any water vapour feed under pressure provided in the reforming process.
  • Such water vapour generally has a pressure comprised between 2 and 100 bar and a temperature comprised between 120 and 600° C.
  • water vapour coming from an external source with respect to the reforming process.
  • a flow comprising light gaseous hydrocarbons such as methane or natural gas is used as gas flow comprising hydrocarbons (flow line 2 ).
  • the flow comprising hydrocarbons is suitably compressed in a compression step represented by block 11 .
  • the block 11 comprises a compressor for the compression of such flow at a pressure preferably comprised between 2 and 100 bar.
  • the gas flow comprising hydrocarbons and water vapour undergoes the reforming step, in which as a result of the various reforming and shift reactions the hydrocarbons are decomposed in basic compounds such as hydrogen, carbon monoxide and carbon dioxide.
  • the gas flow comprising hydrocarbons and water vapour may be preheated up to the reaction temperature in a preliminary heating step, which is not shown in FIG. 1 because it is conventional.
  • block 12 comprises an exchanger type reforming apparatus (or exchanger reformer) of the type shown in FIG. 2 , which is per se known and hence will not be described in details in the following description. Reference is for instance made to EP-A-0 841 301.
  • Such equipment comprises inside it a reaction space filled with catalyst, generally a tube bundle, crossed by the gas flow comprising hydrocarbons and water vapour.
  • a flow comprising, beside hydrogen, inter alias, carbon monoxide and/or carbon dioxide, is obtained.
  • Such flow is indicated by flow line 4 .
  • the gas flow comprising hydrogen coming from the block 12 (flow line 4 ), is in some instances suitably cooled, by means of one or more coolant streams, so as to effectively recover the heat carried by such flow and to allow the condensation of the water vapour therein contained.
  • the water that condenses during this cooling step may be advantageously used as condensate or process water in the process for obtaining the heating fluid according to the present invention, as will be described herein below.
  • the process steps for obtaining the heating fluid according to the present invention are indicated by the blocks 11 , 20 - 24 and by the flow lines 2 , 2 b , 5 - 9 .
  • blocks 20 - 24 indicate a compression step of a gas flow comprising oxygen (block 20 ), a water source (block 21 ), a heating step of a flow comprising oxygen and water (block 22 ), a mixing and combustion step of a gas flow comprising hydrocarbons with a flow comprising oxygen and water vapour (block 23 ) and an expansion step of a heating fluid (block 24 ), respectively.
  • Block 11 corresponding to the compression step of the gas flow comprising hydrocarbons has already been described above with reference to the actual reforming process.
  • the flow lines indicate a gas flow comprising hydrocarbons (flow lines 2 and 2 b ), a gas flow comprising oxygen (flow line 5 ), a flow comprising water (flow line 6 ), a flow comprising oxygen and water (flow line 7 ), a gas flow comprising oxygen and water vapour (flow line 8 ) and a heating fluid (flow line 9 ), respectively.
  • flow line 2 a a portion of the flow 2 coming from the compression step (block 11 ) is mixed with a flow comprising water vapour (flow line 1 ) and fed to the block 12 (flow line 3 ). Whereas the remaining portion of such flow of hydrocarbons (flow line 2 b ) is used as fuel in the block 23 .
  • the portion of gas flow comprising hydrocarbons fed to the reforming step (flow line 2 a ) is twice the portion of such flow fed to the combustion step (flow line 2 b ).
  • air has been used as gas flow comprising oxygen (flow line 5 ).
  • the air flow line 5 which is the comburent in the combustion reaction (block 23 ), is previously compressed in a compression step (block 20 ) to take it to the pressure required for the combustion of the hydrocarbon gas flow.
  • block 20 comprises a compressor for the compression of such flow at a pressure preferably comprised between 2 and 100 bar.
  • flow line 5 the flow comprising oxygen (flow line 5 ) and the flow comprising hydrocarbons are compressed so as to obtain a heating fluid having a pressure substantially equivalent to the pressure of the reactants fed to the reforming equipment (block 12 ).
  • the flow comprising water (flow line 6 ) coming from the water source indicated with the block 21 is advantageously joined to the gas flow comprising air coming from the compression step (block 20 ).
  • the water source may be an external source with respect to the process or, preferably, recovery water coming from other process units, such as the process condensate obtained by cooling the flow comprising hydrogen leaving the reforming step (block 12 ).
  • the water flow coming from the block 21 is advantageously fed at a predetermined pressure to the air flow 5 . More precisely, the water is pumped in the air flow 5 at a pressure substantially equivalent to the pressure of the air itself coming from the block 20 .
  • the flow comprising air and water (flow line 7 ) obtained by joining the flow lines 5 and 6 is advantageously directed to a heating step (block 22 ) for evaporating at least partially the water contained in such flow and obtaining a gas flow comprising air and water vapour (flow line 8 ).
  • the block 22 where the heating step takes place, may comprise one or more conventional heat exchangers, which are not shown.
  • the heating step is carried out in a plurality of heat exchangers arranged in series, so as to increase the heat exchange efficiency.
  • Water evaporation may anyway take place in a following process step, such as in the combustor during the mixing of the comburent with the hydrocarbons or even during the combustion of the hydrocarbons.
  • One or more heat exchangers may be provided for the heating step of the flow 7 .
  • the heating fluid leaving the reforming step (flow line 9 ), may be advantageously used as heating fluid of the flow comprising air and water, as will be described in the following, in a more detailed manner.
  • flow line 8 The gas flow comprising air and water vapour (flow line 8 ) is then mixed with the flow comprising hydrocarbons (flow line 2 b ) inside the block 23 , wherein the combustion step of the hydrocarbons takes place, thus obtaining a high temperature heating fluid (flow line 9 ).
  • the hydrocarbon flow and the flow comprising oxygen may be jointly fed in to the combustor, thus mixing them outside of the latter.
  • the flow comprising water may be fed from the block 21 to the flow comprising hydrocarbons (flow line 2 b ), or directly to the combustor (block 23 ), or even downstream of it, in the high temperature fluid of burnt gases (flow line 9 ).
  • the block 23 where the combustion step takes place, generally comprises a combustor inside which one or more burners for the combustion of the hydrocarbons/air mixture are arranged.
  • the heating fluid (flow line 9 ) from the block 23 is hence employed in the reforming step (block 12 ), as indirect heat source for the reforming of hydrocarbons.
  • the temperature of the heating fluid obtained in the block 23 is generally comprised between 1.400 and 1.800° C., preferably around 1.500° C.
  • the heating fluid is made up of a substantially gaseous flow comprising, inter alias, carbon dioxide, nitrogen and oxygen.
  • the heating fluid further comprises water, preferably in the form of vapour.
  • water preferably in the form of vapour.
  • the heating fluid (flow line 9 ) has a temperature lower than the inlet temperature to the block 12 , having exchanged heat for the reforming reaction of hydrocarbons.
  • Such temperature is anyway high enough (500-800° C.) to enable, according to a preferred embodiment of the present invention, the heating—by indirect heating exchange—and the following evaporation of the water contained in the flow 7 fed to the heating step indicated by the block 22 of FIG. 1 .
  • the heating fluid (flow line 9 ) further cooled is finally expanded in an expansion step (block 24 ) thus accomplishing an advantageous recovery of the compression energy.
  • the block 24 generally comprises at least one turbine for allowing the desired expansion of the heating fluid.
  • the gas flow rate to be expanded in the turbine is remarkably higher than in the prior art, making thus an improvement of the thermodynamic cycle efficiency and therefore a further reduction of the energy consumption possible.
  • heating fluid flow line 9
  • the heating fluid is then vented or condensed in order to recover the water therein contained.
  • the heating fluid be vented, it will have a particularly low content of pollutants, such as nitrogen oxide, as the presence of water in the combustor advantageously reduces the formation of such compounds.
  • pollutants such as nitrogen oxide
  • the gas flow comprising, inter alias, hydrogen and carbon monoxide (flow line 4 ) obtained in the reforming step may be used as basic compound for the chemical synthesis of products such as ammonia, methanol. Or it can be appropriately purified to pure hydrogen and/or carbon monoxide or for any common application.
  • the block 30 schematically indicates the necessary step or steps for the synthesis of the desired product, which comes out from the block 30 through the flow line 31 .
  • the gas flow comprising air (comburent, flow line 5 ) is enriched with water vapour through adiabatic saturation.
  • the combustion process comprises the step of heating the flow comprising water and feeding it at a predetermined pressure into the flow comprising oxygen (flow line 5 ) upstream of the combustor, in such a way to let the water at least partially evaporate and obtain a flow comprising oxygen and water vapour.
  • the way the gas flow comprising air is enriched with water vapour is not particularly critical, as methods might be employed different from what herein described.
  • the hydrocarbon reforming process comprises the steps of:
  • the heating fluid is obtained by means of the above-described process, preferably according to the process described with reference to the example of FIG. 1 .
  • the step of cooling down the heating fluid corresponds to the step of heating the flow comprising air and water shown in FIG. 1 and indicated by the block 22 .
  • the present invention further concerns the use of water, preferably in the form of vapour, in a process for obtaining a heating fluid as indirect heat source for carrying out endothermic reactions, such as the reforming of hydrocarbons.
  • a heating fluid as indirect heat source for carrying out endothermic reactions, such as the reforming of hydrocarbons.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Carbon And Carbon Compounds (AREA)
US09/802,925 2000-03-22 2001-03-12 Process for obtaining a heating fluid as indirect heat source for carrying out reforming reactions Expired - Lifetime US7465324B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP00106237 2000-03-22
EP00106237A EP1136444B1 (en) 2000-03-22 2000-03-22 Process for hydrocarbon reforming
EP00106237.1 2000-03-22

Publications (2)

Publication Number Publication Date
US20010025449A1 US20010025449A1 (en) 2001-10-04
US7465324B2 true US7465324B2 (en) 2008-12-16

Family

ID=8168200

Family Applications (1)

Application Number Title Priority Date Filing Date
US09/802,925 Expired - Lifetime US7465324B2 (en) 2000-03-22 2001-03-12 Process for obtaining a heating fluid as indirect heat source for carrying out reforming reactions

Country Status (17)

Country Link
US (1) US7465324B2 (id)
EP (1) EP1136444B1 (id)
KR (1) KR100824082B1 (id)
CN (1) CN1220622C (id)
AR (1) AR027700A1 (id)
AT (1) ATE556987T1 (id)
AU (1) AU779544B2 (id)
BR (1) BR0101071A (id)
CA (1) CA2341124C (id)
EG (1) EG22750A (id)
GC (1) GC0000275A (id)
ID (1) ID29700A (id)
MX (1) MXPA01002887A (id)
MY (1) MY148606A (id)
NZ (1) NZ510414A (id)
RU (1) RU2283272C2 (id)
UA (1) UA78671C2 (id)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10730749B2 (en) * 2018-11-07 2020-08-04 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for integrating a partial oxidation plant with an oxy-combustion plant utilizing a steam turbine

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080016768A1 (en) 2006-07-18 2008-01-24 Togna Keith A Chemically-modified mixed fuels, methods of production and used thereof
FR2909445B1 (fr) 2006-12-05 2009-02-06 Air Liquide Procede de controle d'une reaction de reformage par mesure de la temperature des tubes de reformage
US8261700B2 (en) * 2008-06-26 2012-09-11 Haldor Topsoe A/S Steam superheater
EP2147896A1 (en) * 2008-07-22 2010-01-27 Uhde GmbH Low energy process for the production of ammonia or methanol
CN102556965B (zh) * 2012-01-13 2013-07-17 清华大学 一种液态碳氢燃料催化重整冷却高温部件的方法
KR20220145650A (ko) * 2021-04-22 2022-10-31 현대자동차주식회사 액화석유가스 개질 시스템의 연소제어장치 및 그 제어방법

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3717129A (en) * 1970-09-28 1973-02-20 Phillips Petroleum Co Method and apparatus for reducing engine exhaust pollutants
US4003343A (en) * 1975-04-04 1977-01-18 Phillips Petroleum Company Method and apparatus for maintaining the operating temperature in a device for reducing engine exhaust pollutants
US4156659A (en) * 1974-12-11 1979-05-29 United States Steel Corporation Method of manufacturing a reducing gas useful in a direct reduction process
US4337170A (en) * 1980-01-23 1982-06-29 Union Carbide Corporation Catalytic steam reforming of hydrocarbons
US4479925A (en) * 1982-09-13 1984-10-30 The M. W. Kellogg Company Preparation of ammonia synthesis gas
US4488866A (en) * 1982-08-03 1984-12-18 Phillips Petroleum Company Method and apparatus for burning high nitrogen-high sulfur fuels
EP0212755A2 (en) 1985-08-30 1987-03-04 Shell Internationale Researchmaatschappij B.V. Process and apparatus for producing synthesis gas
US5011625A (en) * 1989-12-11 1991-04-30 The M. W. Kellogg Company Autothermal steam reforming process
EP0450872A1 (en) 1990-04-03 1991-10-09 The Standard Oil Company Endothermic reaction apparatus
US5122299A (en) * 1989-12-11 1992-06-16 The M. W. Kellogg Company Autothermal steam reforming process
DE4327176C1 (de) 1993-08-13 1995-01-26 Metallgesellschaft Ag Röhrenofen für die Erzeugung kohlenmonoxidhaltiger Gasgemische
DE4340688A1 (de) 1993-11-30 1995-06-01 Uhde Gmbh Verfahren zur Einstellung der Kohlenstoffaktivität in einem Synthesegas-Erzeugungsprozeß
WO2000010912A1 (en) * 1998-08-19 2000-03-02 Methanex Corporation Method for performing a process wherein a feedstock is subjected to an endothermic reaction
US6099922A (en) * 1996-04-06 2000-08-08 Metallgesellschaft Aktiengesellschaft Thermally insulated metal surface protected against metal dusting corrosion
US6170264B1 (en) * 1997-09-22 2001-01-09 Clean Energy Systems, Inc. Hydrocarbon combustion power generation system with CO2 sequestration
US20010033819A1 (en) * 2000-04-13 2001-10-25 Serguei Zhdanok Process for the production of a mixture comprising hydrogen and CO
US6871502B2 (en) * 2002-02-15 2005-03-29 America Air Liquide, Inc. Optimized power generation system comprising an oxygen-fired combustor integrated with an air separation unit

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3717129A (en) * 1970-09-28 1973-02-20 Phillips Petroleum Co Method and apparatus for reducing engine exhaust pollutants
US4156659A (en) * 1974-12-11 1979-05-29 United States Steel Corporation Method of manufacturing a reducing gas useful in a direct reduction process
US4003343A (en) * 1975-04-04 1977-01-18 Phillips Petroleum Company Method and apparatus for maintaining the operating temperature in a device for reducing engine exhaust pollutants
US4337170A (en) * 1980-01-23 1982-06-29 Union Carbide Corporation Catalytic steam reforming of hydrocarbons
US4488866A (en) * 1982-08-03 1984-12-18 Phillips Petroleum Company Method and apparatus for burning high nitrogen-high sulfur fuels
US4479925A (en) * 1982-09-13 1984-10-30 The M. W. Kellogg Company Preparation of ammonia synthesis gas
EP0212755A2 (en) 1985-08-30 1987-03-04 Shell Internationale Researchmaatschappij B.V. Process and apparatus for producing synthesis gas
JPS6253396A (ja) 1985-08-30 1987-03-09 シエル・インタ−ナシヨネイル・リサ−チ・マ−チヤツピイ・ベ−・ウイ 合成ガスの製造方法および装置
US4681701A (en) 1985-08-30 1987-07-21 Shell Oil Company Process for producing synthesis gas
EP0212755A3 (en) 1985-08-30 1990-01-03 Shell Internationale Research Maatschappij B.V. Process and apparatus for producing synthesis gas
US5011625A (en) * 1989-12-11 1991-04-30 The M. W. Kellogg Company Autothermal steam reforming process
US5122299A (en) * 1989-12-11 1992-06-16 The M. W. Kellogg Company Autothermal steam reforming process
EP0450872A1 (en) 1990-04-03 1991-10-09 The Standard Oil Company Endothermic reaction apparatus
DE4327176C1 (de) 1993-08-13 1995-01-26 Metallgesellschaft Ag Röhrenofen für die Erzeugung kohlenmonoxidhaltiger Gasgemische
DE4340688A1 (de) 1993-11-30 1995-06-01 Uhde Gmbh Verfahren zur Einstellung der Kohlenstoffaktivität in einem Synthesegas-Erzeugungsprozeß
US6099922A (en) * 1996-04-06 2000-08-08 Metallgesellschaft Aktiengesellschaft Thermally insulated metal surface protected against metal dusting corrosion
US6170264B1 (en) * 1997-09-22 2001-01-09 Clean Energy Systems, Inc. Hydrocarbon combustion power generation system with CO2 sequestration
WO2000010912A1 (en) * 1998-08-19 2000-03-02 Methanex Corporation Method for performing a process wherein a feedstock is subjected to an endothermic reaction
US20010033819A1 (en) * 2000-04-13 2001-10-25 Serguei Zhdanok Process for the production of a mixture comprising hydrogen and CO
US6871502B2 (en) * 2002-02-15 2005-03-29 America Air Liquide, Inc. Optimized power generation system comprising an oxygen-fired combustor integrated with an air separation unit

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10730749B2 (en) * 2018-11-07 2020-08-04 L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process for integrating a partial oxidation plant with an oxy-combustion plant utilizing a steam turbine

Also Published As

Publication number Publication date
AU779544B2 (en) 2005-01-27
EP1136444B1 (en) 2012-05-09
AR027700A1 (es) 2003-04-09
CN1314304A (zh) 2001-09-26
CN1220622C (zh) 2005-09-28
KR100824082B1 (ko) 2008-04-21
RU2283272C2 (ru) 2006-09-10
NZ510414A (en) 2003-01-31
ATE556987T1 (de) 2012-05-15
KR20010092690A (ko) 2001-10-26
UA78671C2 (en) 2007-04-25
MXPA01002887A (es) 2003-08-20
EP1136444A1 (en) 2001-09-26
MY148606A (en) 2013-05-15
CA2341124C (en) 2010-02-09
US20010025449A1 (en) 2001-10-04
CA2341124A1 (en) 2001-09-22
BR0101071A (pt) 2001-11-06
EG22750A (en) 2003-07-30
ID29700A (id) 2001-09-27
AU2643301A (en) 2001-09-27
GC0000275A (en) 2006-11-01

Similar Documents

Publication Publication Date Title
US12240758B2 (en) Systems and methods for production and separation of hydrogen and carbon dioxide
EP0106076B1 (en) Preparation of ammonia synthesis gas
US6981994B2 (en) Production enhancement for a reactor
KR100201886B1 (ko) 자동열 증기 개질방법
US4681745A (en) Ammonia production process
US4985231A (en) Production of hydrogen-containing gas streams
US20070264186A1 (en) Process for Production of Hydrogen and/or Carbon Monoxide
US20240058780A1 (en) Ammonia decomposition system
US12139405B2 (en) Apparatuses and methods for hydrogen production
US20060216228A1 (en) Hydrogen generation
US20250154016A1 (en) Ammonia synthesis and urea synthesis with reduced co2 footprint
CN115707648B (zh) 生产h2和合成气的工艺
US7465324B2 (en) Process for obtaining a heating fluid as indirect heat source for carrying out reforming reactions
US20140124705A1 (en) Oxy-fuel combustion
NO315938B1 (no) Fremgangsmåte for frembringelse av metanol fra naturgass
US20210269307A1 (en) Carbon recycling in steam reforming process
EP0914294B1 (en) Oxygen and nitrogen injection for increasing ammonia production
NZ203799A (en) Catalytic processes for the production of ammonia
CN100427384C (zh) 一种烃类蒸汽转化制备co和合成气及甲醇的方法
EP4665677A1 (en) A process for production of hydrogen gas
CN115768719A (zh) 用于从尾气回收内能的方法和设备

Legal Events

Date Code Title Description
AS Assignment

Owner name: AMMONIA CASALE S.A., SWITZERLAND

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:FILIPPI, ERMANNO;REEL/FRAME:011610/0665

Effective date: 20010221

STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 12TH YR, SMALL ENTITY (ORIGINAL EVENT CODE: M2553); ENTITY STATUS OF PATENT OWNER: SMALL ENTITY

Year of fee payment: 12